CN105294374A - Method for preparing paraxylene and propylene by methanol and/or dimethyl ether - Google Patents
Method for preparing paraxylene and propylene by methanol and/or dimethyl ether Download PDFInfo
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- CN105294374A CN105294374A CN201410245420.6A CN201410245420A CN105294374A CN 105294374 A CN105294374 A CN 105294374A CN 201410245420 A CN201410245420 A CN 201410245420A CN 105294374 A CN105294374 A CN 105294374A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The invention relates to a method for preparing paraxylene and propylene by methanol and/or dimethyl ether. The method comprises the following steps: carrying out aromatization reaction on the the methanol and/or the dimethyl ether; carrying out alkylation reaction on ethylene, the methanol and/or the dimethyl ether; and coupling the two reactions. According to the method disclosed by the invention, components rich in ethylene in reaction by-products during preparation of the paraxylene by the methanol and/or the dimethyl ether in the presence of a catalyst are returned to a reaction system, then the alkylation reaction is carried out on the components, the methanol and/or the dimethyl ether, and the paraxylene and the propylene can be produced in a high-selectivity mode.
Description
Technical field
The present invention relates to a kind of method of methyl alcohol and/or dme reaction p-Xylol processed and propylene, belong to chemical field.
Background technology
P-Xylol (PX) and propylene are all important basic chemical raw materials.At present, p-Xylol mainly obtains through Aromatic Hydrocarbon United Plant, first petroleum naphtha is obtained reformed oil containing aromatic hydrocarbons by CONTINUOUS REFORMER, then obtain PX product to greatest extent through unit such as Aromatics Extractive Project, aromatic hydrocarbons fractionation, disproportionation and transalkylation, xylene isomerization and fractionation by adsorption.Because p-Xylol is subject to thermodynamic control at the content of three isomer, p-Xylol is at C
8only account for about 23% in BTX aromatics, so Matter Transfer treatment capacity is large in whole PX production process, equipment is huge, and process cost is high.Particularly the boiling point difference of dimethylbenzene three isomer is very little, adopts common distillation technique can not obtain high purity p-Xylol, and must adopt expensive adsorptive separation technology.Propylene is mainly derived from the byproduct that petroleum refinery and naphtha steam cracking produce ethene, or with the obtained propane of natural gas processing for raw material is produced.P-Xylol mainly for the production of polyester, propylene mainly for the preparation of polypropylene, vinyl cyanide and the 1,3-PD produced needed for polyester, along with the fast development of global economy, as the p-Xylol of chemical industry basic raw material and the demand also cumulative year after year of propylene.
Methanol is the new way that Non oil-based route produces aromatic hydrocarbons for aromatic hydrocarbons.Chinese patent CN101244969 discloses a kind of C
1-C
2the fluidizer of hydro carbons or aromatization of methanol and catalyst regeneration, utilizes this device and catalyzer, can regulate the coking state of the catalyzer in aromatization reactor at any time, thus reaches continuous high-efficient conversion C
1-C
2hydro carbons or methyl alcohol highly selective generate the object of aromatic hydrocarbons.Chinese patent CN1880288 discloses a kind of process of methanol conversion for preparing arene, and in ZSM-5 Type Zeolites agent, methanol oxidation is converted into the product based on aromatic hydrocarbons, and the overall selectivity with aromatic hydrocarbons is high, and technological operation is advantage flexibly.US Patent No. 4615995 discloses a kind of ZSM-5 molecular sieve catalyzer having supported Zn and Mn, for preparing olefin through methanol conversion and aromatic hydrocarbons, can be changed the ratio of low-carbon alkene/aromatic hydroxy compound in product by the content of Zn and Mn in regulating catalyst.
Methanol-to-olefins and preparing propylene from methanol are the new ways that Non oil-based route produces ethene, propylene.Within 1976, MobilOil company has carried out the reaction that methyl alcohol is converted into hydrocarbon polymer on ZSM-5 molecular sieve catalyzer.USP4,035, disclose the process that methyl alcohol transforms gasoline on ZSM-5 molecular sieve catalyzer in 430; USP4,542, disclose the technology of methyl alcohol preparing low-carbon olefins on ZSM-5 molecular sieve catalyzer in 252; USP3,911,041, USP4,049,573, USP4, disclose in 100,219, JP60-126233, JP61-97231 and JP62-70324 use phosphorus, magnesium, silicon or alkali metal modification ZSM-5 molecular sieve catalyzer by the reaction of preparing low carbon olefinic hydrocarbon with methanol; USP5,367, disclosing Dalian Chemical Physics Research Institute in 100 uses the ZSM-5 molecular sieve catalyzer of phosphorus and lanthanum modification by the reaction of methyl alcohol or methyl alcohol and/or dme preparing low-carbon olefins, its ethene and propylene overall selectivity are only about 65wt%, and ethene, propylene and butylene overall selectivity are greater than 85wt%.
CN101767038B and CN101780417B discloses a kind of Methanol p-Xylol co-producing light olefins catalyzer and method, points out to achieve on metal and silylating reagent catalyzer the object directly being produced three large basic chemical ethene, propylene and p-Xylol in a reaction process by methyl alcohol.In reaction gained hydrocarbon product, the selectivity of p-Xylol in aromatic hydrocarbons is greater than more than 80wt%, and ethene and propylene are at C
1-C
5in lower carbon number hydrocarbons, selectivity is greater than more than 80wt%.But the drawback of the method be to obtain highly purified ethylene product must by cold separation technology, investment and energy consumption all comparatively greatly, directly affects the economy of this process.
In addition, CN101780417B relates to the method for preparing paraxylene by methyl alcohol conversion and low-carbon alkene (ethene and propylene), does not wherein relate in order to further propylene enhancing avoids the difficulty of ethylene separation, will be rich in the C of ethene
2 -component freshening further with the process of methanol alkylation propylene enhancing.CN102464550A discloses a kind of method of co-producing light olefins and p-Xylol, described method for comprising carbon four, carbon five hydrocarbon enters the first reaction zone alkene, this is C
4or liquefied gas cracking olefin hydrocarbon, wherein do not relate to the process of ethene and methanol/dimethyl ether alkylation propylene yet.
Summary of the invention
The object of this invention is to provide a kind of method of methyl alcohol and/or dimethyl ether p-Xylol and propylene.
For this reason, the invention provides a kind of method of methyl alcohol and/or dimethyl ether p-Xylol and propylene, comprise the following steps:
A) raw material containing methyl alcohol and/or dme is reacted with catalyst exposure in reactive system; By the described reactive system C being rich in ethene out
2 -component returns described reactive system, and continues over the catalyst to react to generate propylene with raw material;
B) from described reactive system C out
6 +component, is isolated to product p-Xylol; With
C) from described reactive system C out
3component is isolated to product propylene.
In a preferred embodiment, described reactive system comprises the first reaction zone and second reaction zone, and said method comprising the steps of:
A) first the raw material containing methyl alcohol and/or dme to be contacted with catalyst I by the first reaction zone aromatization occurs, then enter second reaction zone and contact with catalyst I I and alkylationization occurs react; By the described second reaction zone C being rich in ethene out
2 -component returns to described second reaction zone, and alkylated reaction occurs on described catalyst I I to generate propylene with the methyl alcohol in described second reaction zone and/or dme;
B) C out from described second reaction zone
6 +component obtains product p-Xylol through being separated further; With
C) C out from described second reaction zone
3component obtains propylene through being separated further.
In a preferred embodiment, described reactive system comprises the first reaction zone and second reaction zone, and said method comprising the steps of:
A) first to be contacted with catalyst I by the first reaction zone by the raw material containing methyl alcohol and/or dme aromatization occurs, obtain resultant A, described resultant A, after separation system separation, is rich in the C of ethene
2 -component turns back to described second reaction zone, and on catalyst I I, carries out alkylated reaction with enter into second reaction zone methyl alcohol and/or dme, obtains resultant B; The C being rich in ethene in resultant A and resultant B
2 -component continues to turn back to second reaction zone, and to contact at catalyst I I with the methyl alcohol in second reaction zone and/or dme and alkylated reaction occurs to generate propylene;
B) C in described resultant A and resultant B
6 +component obtains product p-Xylol through being separated further; With
C) C in described resultant A and resultant B
3component obtains product propylene through being separated further.
In a preferred embodiment, described catalyzer, described catalyst I and catalyst I I contain identical or different modified zeolite molecular sieve catalyzer.
In a preferred embodiment, described modified zeolite molecular sieve catalyzer is obtained through precious metal and rare-earth metal modified and silicone-based compound modification by ZSM-5 and/or ZSM-11 zeolite molecular sieve.
In a preferred embodiment, in described modified zeolite molecular sieve catalyzer, the content of described precious metal is the 0.1-10wt% of described total catalyst weight.
In a preferred embodiment, the content of described rare earth metal is the 0.1-5wt% of described total catalyst weight.
In a preferred embodiment, the Si amount supported by silicone-based compound modification is the 1-10wt% of the gross weight of described modified zeolite molecular sieve catalyzer.
In a preferred embodiment, described precious metal is silver; Described rare earth metal is lanthanum.
In a preferred embodiment, the silicone-based compound that described silicone-based compound modification adopts, structural formula is shown below:
Wherein R
1, R
2, R
3and R
4c independently of one another
1-10alkyl.
In a preferred embodiment, described silicone-based compound is tetraethoxy.
In a preferred embodiment, described reaction zone comprises a reactor or multiple reactor connected by series connection and/or parallel way; And one or more preferably, in the optional self-retaining bed of described reactor, fluidized-bed and moving-burden bed reactor.
In a preferred embodiment, described first reaction zone and described second reaction zone are in same reactor; And one or more preferably, in the optional self-retaining bed of described reactor, fluidized-bed and moving-burden bed reactor.
In a preferred embodiment, described first reaction zone comprises a reactor or multiple reactor connected by series connection and/or parallel way; Described second reaction zone comprises a reactor or multiple reactor connected by series connection and/or parallel way; And between described first reaction zone and described second reaction zone, connected by the mode of serial or parallel connection; And one or more preferably, in the optional self-retaining bed of described reactor, fluidized-bed and moving-burden bed reactor.
Beneficial effect of the present invention includes but not limited to following aspect: the invention provides a kind of with the novel method of methyl alcohol and/or dimethyl ether p-Xylol and propylene, wherein by by the C being rich in ethene in reaction product
2 -component freshening and methyl alcohol and/or dme generation alkylated reaction generate propylene further, final acquisition highly selective p-Xylol and propylene, avoid the high expense that ethylene product is separated on the one hand, the propylene product with the larger market requirement can be increased production further on the other hand, thus effectively can improve the economy of this technology.
Accompanying drawing explanation
Fig. 1 is the schema of the method according to one embodiment of this invention.
Fig. 2 is the schema of the method according to another embodiment of the present invention.
Fig. 3 is the schema of the method according to another embodiment of the present invention.
Fig. 4 is the schema of the method according to another embodiment of the present invention.
Embodiment
In the method for the invention, methyl alcohol and/or dme aromatization, ethene are coupled with methyl alcohol and/or dme alkylated reaction two reaction process, simultaneously high selectivity production of para-xylene and propylene.Particularly, first material benzenemethanol and/or dme contact with catalyzer (catalyzer is present in reactor) and carry out aromatization in reactive system, and the product of generation enters separation system (such as separation column etc.) and is separated; After separation system is separated, obtain C
6 +component (carbon number equals the aromatic hydrocarbons being greater than 6), C
4-C
5component (carbon number is the hydro carbons of 4 and 5), C
3component (propylene and propane that carbon number equals 3) and be rich in the C of ethene
2 -(carbon number is less than or equal to hydro carbons and CO, CO of 2 to component
2and H
2) and water (H
2o), wherein, the C of ethene is rich in
2 -component Returning reacting system, C
6 +component obtains p-Xylol, C through being separated (such as rectifying tower, Crystallization Separation system etc.) further
3component obtains propylene through being separated (such as rectifying tower etc.) further, and a small amount of C
4-C
5component and H
2for other object after O collects.Wherein said reactive system can be an independent reaction zone, also can be the combination of two or more reaction zone, and multiple reaction zone can, in same reactor, also can be respectively in the reactor of multiple serial or parallel connection.Preferably, described reactor be in fixed bed, fluidized-bed or moving-bed any one or several arbitrarily.
In a preferred embodiment, according to a kind of reaction process of method of the present invention as shown in Figure 1.In FIG, reactive system is made up of a reactor with a reaction zone, and wherein material benzenemethanol and/or dme react with catalyst exposure wherein in the reaction zone of this reactive system, and the product of generation, after separation system is separated, obtains C
6 +component, C
4-C
5component, C
3component and C
2 -component (comprises the C being rich in ethene
2 -component and periodic off-gases) and H
2o, wherein, is rich in the C of ethene
2 -component Returning reacting system, C
6 +component obtains p-Xylol, C through being separated further
3component obtains propylene through being separated further.
In a preferred embodiment, according to a kind of reaction process of method of the present invention as shown in Figure 2.In fig. 2, reactive system is made up of a reactor with two reaction zones, the main reaction of the first reaction zone is methyl alcohol and/or dme aromatization, and the main reaction of second reaction zone is ethene (by product of the first reaction zone) and methyl alcohol and/or dme alkylated reaction.Material benzenemethanol and/or dme first by the first reaction zone and with catalyst I contact reacts wherein, then by second reaction zone and with catalyst I I contact reacts wherein, the product of generation enters separation system and is separated; C is obtained after separation system is separated
6 +component, C
4-C
5component, C
3component and C
2 -component (comprises the C being rich in ethene
2 -component and periodic off-gases) and H
2o, is wherein rich in the C of ethene
2 -component return to second reaction zone and with enter the methyl alcohol of second reaction zone and/or dme and to contact with catalyst I I and carry out alkylated reaction; C
6 +component obtains p-Xylol, C through being separated further
3component is separated further and obtains propylene.
In a preferred embodiment, according to a kind of reaction process of method of the present invention as shown in Figure 3.In figure 3, reactive system is made up of the two reaction zones respectively in two reactors in parallel, the main reaction of the first reaction zone is methyl alcohol and/or dme aromatization, and the main reaction of second reaction zone is ethene (by product of the first reaction zone) and methyl alcohol and/or dme alkylated reaction.First methyl alcohol and/or dme contact with catalyst I in reaction zone and carry out aromizing and generate product A, and product A enters separation system and is separated; The C being rich in ethene obtained after separation
2 -component turns back to second reaction zone, carries out alkylated reaction generate product B with the methyl alcohol and/or dme that enter into second reaction zone on catalyst I I, and product B enters separation system and is separated; After separation system is separated, be wherein rich in the C of ethene
2 -component turns back to second reaction zone, and the C that wherein said product A and product B obtain after separation system is separated
6 +component obtains p-Xylol, C through being separated further
3component is separated further and obtains propylene.
In a preferred embodiment, according to a kind of reaction process of method of the present invention as shown in Figure 4.In the diagram, except reactive system is made up of the two reaction zones respectively in same reactor, its reaction process is identical about the process described by Fig. 3 with above-mentioned, repeats no more here, and such reactive system can be realized by multistage feeding.
In the present invention, the catalyzer used is for ZSM-5 and/or ZSM-11 zeolite molecular sieve is through precious metal and rare earth metal combined modified and the modified ZSM-5 obtained through silicone-based compound finishing and/or ZSM-11 zeolite [molecular sieve.When reaction zone is two, be present in described catalyst I wherein respectively and catalyst I I can for identical or different catalyzer.Such as, in a preferred embodiment, described catalyst I and catalyst I I are same catalyzer or identical catalyzer.More preferably, the described catalyzer, catalyst I or the catalyst I I that use in the present invention are after silicone-based compound finishing, and the loading of Si is the 1-10wt% of this total catalyst weight.
In a preferred embodiment, the preparation process of the catalyzer of the present invention's use is as follows:
(1) by former for ZSM-5 and/or ZSM-11 zeolite molecular sieve powder through NH
4 +ion-exchange, roasting are prepared into acidic zeolite.
(2) above-mentioned acidic zeolite is immersed in the soluble salt solutions of precious metal and rare earth metal, obtains metal-modified zeolite molecular sieve.
(3) use Siloxane based agents to carry out finishing to above-mentioned metal modified zeolites molecular sieve, further modulation molecular sieve outer surface acidity and pore structure, obtain modified zeolite molecular sieve catalyzer.
Preferably, the described catalyzer, catalyst I or the catalyst I I that use in the present invention through precious metal and rare earth metal combined modified after, bullion content is the 0.1-10wt% of this total catalyst weight; Rare earth metal content is the 0.1-5wt% of this total catalyst weight.
Preferably, the precious metal used in the present invention is silver; Rare earth metal is lanthanum, and it uses with the form of their soluble salt.
Preferably, the silicone-based compound used in the present invention is shown below:
Wherein R
1, R
2, R
3and R
4c independently of one another
1-10alkyl, as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl and octyl group, and their isomeric forms.
Preferably, the silicone-based compound of use is tetraethyl orthosilicate.
Preferably, in the present invention described first reaction zone and second reaction zone all can use fixed bed reaction technique, can be combined simultaneously adopt fluidized-bed or moving bed reaction technique with revivifier.Described first reaction zone and second reaction zone can be respectively in a reactor or in the identical or different reactor of multiple serial or parallel connection, are realized by multistage feeding.
In the methods of the invention, methyl alcohol and/or dme aromatization, ethene and methyl alcohol and/or dme alkylated reaction temperature are within the scope of 300-600 DEG C, and methyl alcohol and/or the preferred temperature of reaction of dme aromatization are 450-520 DEG C, ethene and methyl alcohol and/or dme alkylated reaction preferable reaction temperature are 350-500 DEG C.
In the methods of the invention, methyl alcohol and/or dme aromatization feedstock quality air speed count 0.1-10h with methyl alcohol and/or dme
-1, be preferably 1-5h
-1.Wherein ethene and methyl alcohol and/or dme mol ratio are selected arbitrarily within the scope of 0.1-10, are generally preferably 0.5-5.
In the present invention, described C
2 -component refers to that in molecular formula, carbonatoms is less than or equal to the component of 2, comprises ethene and ethane, methane, CO, CO
2and H
2deng, i.e. C
2 -component comprises the C being rich in ethene
2 -component and periodic off-gases.Periodic off-gases is mainly ethane, methane, CO, CO
2and H
2deng.
In the present invention, described C
3component refers to the compound that in molecular formula, carbonatoms equals 3, comprises propylene, propane etc.
In the present invention, described C
4-C
5component refers to the component that in molecular formula, carbonatoms equals 4,5, comprises Trimethylmethane, iso-butylene, butane, 1-butylene, 2-butylene, iso-pentane, neopentane, pentane, 1-amylene, 2-penta rare etc.
In the present invention, described C
6 +component refers to that in molecular formula, carbonatoms is more than or equal to the component of 6, comprises p-Xylol and other fragrant hydrocarbons and their derivates etc.
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to these embodiments.
Gas chromatograph on-line analysis product forms, and analysis condition is:
Chromatogram model: VarianCP3800
Chromatographic column: CPWax52CB capillary chromatographic column
Carrier gas: helium, 5ml/min
Post case temperature: 60-220 DEG C, temperature programming, 15 DEG C/min
Injector temperature: 260 DEG C
Detector: flame ionization ditector (FID)
Detector temperature: 300 DEG C
Embodiment 1
the preparation of catalyzer: silver-colored lanthanum and silane-modified HZSM-5 molecular sieve catalyst and HZSM-11
molecular sieve catalyst
1) by former for 500gZSM-5 zeolite molecular sieve powder (Fushun Petrochemical Company catalyst plant) (SiO
2/ Al
2o
3=68) and the former powder of 500gZSM-11 zeolite molecular sieve (Catalyst Factory, Nankai Univ) (SiO
2/ Al
2o
3=50) at 550 DEG C, template is removed in roasting respectively, exchange is carried out 4 times with 0.5 molar equivalent ammonium nitrate solution in 80 DEG C of water-baths, dry in 120 DEG C of air after exchange, at 550 DEG C, roasting 3 hours, obtains HZSM-5, HZSM-11 zeolite molecular sieve respectively.
2) step 1 is got respectively) HZSM-5 and the HZSM-11 zeolite molecular sieve 100g compression molding prepared, after crushing and screening, obtain 40-60 order sample, with the Silver Nitrate (AgNO of 6% mass concentration
3) solution normal temperature dipping 4 hours, incline and 120 DEG C of oven dry after supernatant liquid, roasting 6 hours in 550 DEG C of air, obtains silver-colored modification Ag-HZSM-5 and Ag-HZSM-11 zeolite molecular sieve.
3) respectively by step 2) Ag-HZSM-5 and the Ag-HZSM-11 zeolite molecular sieve 5wt% lanthanum nitrate hexahydrate (La (NO that obtains
3)
36H
2o) normal temperature dipping 4 hours, inclines and 120 DEG C of oven dry after supernatant liquid, roasting 6 hours in 550 DEG C of air, obtains silver and combined modified Ag-La-HZSM-5 and the Ag-La-HZSM-11 zeolite molecular sieve of lanthanum.
4) tetraethoxy (TEOS) normal temperature dipping step 3 is adopted respectively) Ag-La-HZSM-5 and the Ag-La-HZSM-11 zeolite molecular sieve that obtains 24 hours, roasting in 120 DEG C of oven dry, 550 DEG C of air of inclining after supernatant liquid obtains HZSM-5 and the HZSM-11 molecular sieve catalyst of silver-colored lanthanum and silylating reagent for 6 hours, and catalyzer is called after MTPP-08 and MTPP-09 respectively.XRF diffraction (XRF) analysis measures each element loading of MTPP-08 and MTPP-09 catalyzer, and on MTPP-08 catalyzer, Ag loading is 1.02wt%, La loading is 1.25wt%, and silanization Si loading thinks 2.32wt%; On MTPP-09 catalyzer, Ag loading is 1.13wt%, La loading is 1.18wt%, and silanization Si loading thinks 2.16wt%.
Embodiment 2
with Methanol p-Xylol and propylene
Reaction process according to Fig. 2, by MTPP-08 catalyzer first reaction zone that is respectively charged into fixed reactor of preparation in embodiment 1 and second reaction zone (each reaction zone is 10 grams).Aromatization of methanol reaction is mainly carried out in first reaction zone, and reaction after product enters second reaction zone, and methanol feeding mass space velocity is 2h
-1, temperature of reaction is 500 DEG C.The C being rich in ethene wherein in distribution of reaction products
2 -component and methyl alcohol jointly enter second reaction zone and react, and wherein ethene/methyl alcohol (mol ratio) is 1/1, and temperature of reaction is 400 DEG C, and ethene and methanol alkylation reaction are carried out in second reaction zone.
Adopt gas chromatograph on-line analysis first reaction zone and second reaction zone mix products composition, the products distribution removed after generating water is as shown in table 1, then removes C
2 -return component after product slates as shown in table 2.
As can be seen from Table 2, C is removed in the first reaction zone and second reaction zone gross product
2 -after component, in product, Propylene Selectivity is 42.52wt%, and Selectivity for paraxylene is 38.05wt%, and propylene and p-Xylol overall selectivity are 80.57wt%.The selectivity of p-Xylol in xylene isomer is 98.98wt%.
Table 1
* wt%, products weight per-cent forms, lower same.
Table 2
Embodiment 3
with Methanol p-Xylol and propylene
Reaction process according to Fig. 3 or 4, is respectively charged into the first reaction zone and second reaction zone (each reaction zone is 10 grams) by MTPP-08 and the MTPP-09 catalyzer of preparation in embodiment 1.Aromatization of methanol reaction is carried out in first reaction zone, and methanol feeding mass space velocity is 2h
-1, temperature of reaction is 500 DEG C.Ethene and methanol alkylation reaction are carried out in second reaction zone, according to the C being rich in ethene in the reaction of methanol conversion products distribution in comparative example
2 -component and methyl alcohol jointly enter second reaction zone and react, and wherein ethene/methyl alcohol (mol ratio) is 1/1, and temperature of reaction is 400 DEG C.
Adopt gas chromatograph on-line analysis first reaction zone and second reaction zone mix products composition, the products distribution removed after generating water is as shown in table 3, then removes C
2 -product slates after component is as shown in table 4.
As can be seen from Table 4, C is removed in the first reaction zone and second reaction zone gross product
2 -after component, in product, Propylene Selectivity is 53.62wt%, and Selectivity for paraxylene is 30.59wt%, and propylene and p-Xylol overall selectivity are 84.21wt%.The selectivity of p-Xylol in xylene isomer is 99.32wt%.
Table 3
Table 4
Comparative example 1
with Methanol p-Xylol co-production propylene, but without C
2
-
the further reaction that component returns
Get in the MTPP-08 catalyzer loading reactor of preparation in 10 grams of embodiments 1 and carry out the reaction of methanol conversion, methanol quality air speed is 2h
-1, temperature of reaction is 500 DEG C.Adopt gas chromatograph on-line analysis product composition, the products distribution removed after generating water is as shown in table 5.
When the independent methanol feeding reaction of reactor, in product, the selectivity of propylene is only 29.48wt%.
Table 5 the reaction of methanol conversion result
Below to invention has been detailed description, but the present invention is not limited to embodiment described herein.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, other changes and distortion can be made.Scope of the present invention is defined by the following claims.
Claims (10)
1. a method for methyl alcohol and/or dimethyl ether p-Xylol and propylene, said method comprising the steps of:
A) raw material containing methyl alcohol and/or dme is reacted with catalyst exposure in reactive system; From the described reactive system C being rich in ethene out
2 -component returns described reactive system, and continues over the catalyst to react to generate propylene with described raw material;
B) from described reactive system C out
6 +component, is isolated to product p-Xylol; With
C) from described reactive system C out
3component is isolated to product propylene.
2. method according to claim 1, is characterized in that, described reactive system comprises the first reaction zone and second reaction zone, and said method comprising the steps of:
A) first the raw material containing methyl alcohol and/or dme to be contacted with catalyst I by described first reaction zone aromatization occurs, then enter described second reaction zone and contact with catalyst I I alkylated reaction occurs; The C being rich in ethene out from described second reaction zone
2 -component returns to described second reaction zone, and alkylated reaction occurs on described catalyst I I to generate propylene with the methyl alcohol in described second reaction zone and/or dme;
B) C out from described second reaction zone
6 +component obtains product p-Xylol through being separated further; With
C) C out from described second reaction zone
3component obtains propylene through being separated further.
3. method according to claim 1, is characterized in that, described reactive system comprises the first reaction zone and second reaction zone, and said method comprising the steps of:
A) first to be contacted with catalyst I by described first reaction zone by the raw material containing methyl alcohol and/or dme aromatization occurs, obtain resultant A, described resultant A, after separation system is separated, is rich in the C of ethene
2 -component turns back to described second reaction zone, and on catalyst I I, carries out alkylated reaction with enter into described second reaction zone methyl alcohol and/or dme, obtains resultant B; The C being rich in ethene in described resultant A and resultant B
2 -component continues to turn back to described second reaction zone, and alkylated reaction occurs on described catalyst I I to generate propylene with the methyl alcohol in described second reaction zone and/or dme;
B) C in described resultant A and resultant B
6 +component obtains product p-Xylol through being separated further; With
C) C in described resultant A and resultant B
3component obtains product propylene through being separated further.
4. the method according to claim 1,2 or 3, is characterized in that, described catalyzer, described catalyst I and described catalyst I I contain identical or different modified zeolite molecular sieve catalyzer.
5. method according to claim 4, is characterized in that, described modified zeolite molecular sieve catalyzer is obtained through precious metal and rare-earth metal modified and silicone-based compound modification by ZSM-5 and/or ZSM-11 zeolite molecular sieve.
6. method according to claim 5, is characterized in that, the structural formula of the silicone-based compound that described silicone-based compound modification adopts is as follows:
Wherein R
1, R
2, R
3and R
4c independently of one another
1-10alkyl.
7. method according to claim 1, is characterized in that, described reactive system comprises a reactor or multiple reactor connected by series connection and/or parallel way.
8. method according to claim 2, is characterized in that, described first reaction zone and described second reaction zone are in same reactor.
9. method according to claim 3, is characterized in that, described first reaction zone comprises a reactor or multiple reactor connected by series connection and/or parallel way; Described second reaction zone comprises a reactor or multiple reactor connected by series connection and/or parallel way; And connected by serial or parallel connection mode between described first reaction zone and described second reaction zone.
10. the method according to claim 7,8 or 9, is characterized in that, described reactor be selected from fixed bed, fluidized-bed and moving-burden bed reactor one or more.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111187134A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing paraxylene and co-produced gasoline from methanol and/or dimethyl ether |
| CN111187133A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing p-xylene and co-producing ethylbenzene and propylene from methanol and/or dimethyl ether and benzene |
| CN111187132A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing gasoline and co-producing p-xylene from methanol and/or dimethyl ether |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177374A (en) * | 2006-11-07 | 2008-05-14 | 中国科学院大连化学物理研究所 | Method for producing propylene by carbinol or dimethyl ether |
| CN101602643A (en) * | 2009-07-24 | 2009-12-16 | 中国海洋石油总公司 | A kind of methyl alcohol/dimethyl ether conversion is produced the method for ethylene and propylene and co-producing p-Xylol |
| CN101607858A (en) * | 2009-07-24 | 2009-12-23 | 中国海洋石油总公司 | The method of a kind of methyl alcohol/dimethyl ether production aromatic hydrocarbons and propylene simultaneously |
-
2014
- 2014-06-04 CN CN201410245420.6A patent/CN105294374B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177374A (en) * | 2006-11-07 | 2008-05-14 | 中国科学院大连化学物理研究所 | Method for producing propylene by carbinol or dimethyl ether |
| CN101602643A (en) * | 2009-07-24 | 2009-12-16 | 中国海洋石油总公司 | A kind of methyl alcohol/dimethyl ether conversion is produced the method for ethylene and propylene and co-producing p-Xylol |
| CN101607858A (en) * | 2009-07-24 | 2009-12-23 | 中国海洋石油总公司 | The method of a kind of methyl alcohol/dimethyl ether production aromatic hydrocarbons and propylene simultaneously |
Non-Patent Citations (1)
| Title |
|---|
| 朱志荣: ""ZSM-5分子筛择形功能的化学修饰及其对二甲苯催化合成的研究"", 《中国优秀博硕士学位论文全文数据库 (博士) 工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111187134A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing paraxylene and co-produced gasoline from methanol and/or dimethyl ether |
| CN111187133A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing p-xylene and co-producing ethylbenzene and propylene from methanol and/or dimethyl ether and benzene |
| CN111187132A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing gasoline and co-producing p-xylene from methanol and/or dimethyl ether |
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